Charge Transfer Effects Research Articles

Effect of Na atom adsorption on the electronic structure of F-doped modified MoTe2 systems in the presence of an electric field: first principles

Abstract The effect of electronic structure and charge transfer on the adsorption of alkali metal sodium atoms by halogen-fluorine atom doped molybdenum ditelluride (MoTe2) has been investigated using a first-principles approach. It was found that the molybdenum ditelluride system underwent a direct bandgap semiconductor-to-metal transition after doping with halogen fluorine atoms. Upon adsorption of alkali metal Na atoms, the conduction band of the F-MoTe2 system shifts from metal to direct bandgap semiconductor. This semiconductor-to-metal-to-semiconductor bandgap modulation method can be well applied to photovoltaics. In addition, we discuss three potential adsorption sites: the hollow site (H), the bridge site (B) and the top site (T). The results showed that all three adsorption sites could be stabilized for adsorption. Subsequently, we selected the most stable B site and applied an electric field ranging from −0.5 eV Å−1 to 0.5 eV Å−1 to the system. At an electric field strength of −0.5 eV Å−1, the system transforms from a direct bandgap semiconductor to a metal. In terms of density of states, F-s, F-p, Te-s, Te-p, and Mo-d pass the Fermi energy level, increasing carrier concentration. It is hoped that these studies will play an important role in improving the photoelectric conversion efficiency.

Encapsulating Proton Inside C60 Fullerene: A Density Functional Theory Study on the Electronic Properties of Cationic X+@C60 (X+ = H+, H3O+ and NH4+)

Confining protons into an enclosed carbon cage is expected to give rise to unique electronic properties for both the inner proton and the outer cage. In this work, we systematically investigated the geometric and electronic structures of cationic X+@C60 (X+ = H+, H3O+, and NH4+), and their corresponding neutral species (X = H2O, NH3), by quantum chemical density functional theory calculations. We show that C60 can trap H2O, NH3, H3O+ and NH4+ at the cage center and only slightly influence their geometries. The single proton clings to the inner wall of C60, forming a C-H chemical bond. The encapsulated neutral species almost do not change the electronic structure of the C60, while the internal cations have obvious effects. The charge transfer effect from the inner species to the C60 cage was found for all X@C60 (X = H2O, NH3) (about 0.0 e), X+@C60 (X+ = H3O+, NH4+) (about 0.5 e) and H+@C60 (about 1.0 e) systems. Encapsulating different forms of protons also regulates the fundamental physico-chemical properties of the hollow C60, such as the HOMO-LUMO gaps, infrared spectra, and electrostatic potential, etc., which are discussed in detail. These findings provide a theoretical insight into protons’ applications, especially in energy.

Carborane-based BODIPY dyes: synthesis, structural analysis, photophysics and applications

Icosahedral boron clusters-based BODIPY dyes represent a cutting-edge class of compounds that merge the unique properties of boron clusters with the exceptional fluorescence characteristics of BODIPY dyes. These kinds of molecules have garnered substantial interest due to their potential applications across various fields, mainly including optoelectronics, bioimaging, and potential use as boron carriers for Boron Neutron Capture Therapy (BNCT). Carborane clusters are known for their exceptional stability, rigid geometry, and 3D-aromaticity, while BODIPY dyes are renowned for their strong absorption, high fluorescence quantum yields, and photostability. The integration of carborane into BODIPY structures leverages the stability and versatility of carboranes while enhancing the photophysical properties of BODIPY-based fluorophores. This review explores the synthesis and structural diversity of boron clusters-based BODIPY dyes, highlighting how carborane incorporation can lead to significant changes in the electronic and optical properties of the dyes. We discuss the enhanced photophysical characteristics, such as red-shifted absorption and emission poperties, charge and electronic transfer effects, and improved cellular uptake, resulting from carborane substitution. The review also delves into the diverse applications of these compounds. In bioimaging, carborane-BODIPY dyes offer superior fluorescence properties and cellular internalization, making them ideal for cell tracking. In photodynamic therapy, (PDT) these dyes can act as potent photosensitizers capable of generating reactive oxygen species (ROS) for targeted cancer treatment making them excellent candidates for PDT. Additionally, their unique electronic properties make them suitable candidates for optoelectronic applications, including organic light-emitting diodes (OLEDs) and sensors. Overall, carborane-BODIPY dyes represent a versatile and promising class of materials with significant potential for innovation in scientific and technological applications. This review aims to provide a comprehensive overview of the current state of research on carborane-BODIPY dyes, highlighting their synthesis, properties, and broad application spectrum.

A Multipole-Based Reactive Force Field for Hydrocarbons.

The computational complexity of quantum chemistry methods has prompted the development of reactive force fields, facilitating practical applications of molecular dynamics simulations for large-scale reactive systems. Current reactive force fields typically employ intricate corrections based on prior chemical knowledge, which severely impedes their further advancement. This study presents a new atomic multipole-based reactive model with bond free (OPERATOR). The force field is constructed on a simple, physically motivated model within the AMOEBA framework that closely resembles the physical representation of the chemical reaction processes. In the force field, the atomic multipoles are generated dynamically according to the atomic environments, aiming to effectively capture significant changes in the electrostatic environments during chemical reactions. Subsequently, atomic multipole-based charge penetration, polarization, and charge transfer effects are incorporated into the force field to describe the complex electrostatic interactions in the system. The force field also includes van der Waals interactions and three-body potentials. In addition, to extend these nonreactive interactions to chemical reactions, the atom distribution multipole moments are used to characterize different chemical environments. The force field has been optimized using the dataset of potential energy surfaces (PESs) of hydrocarbons derived from DFT results of millions of conformations with six degrees of freedom (DOFs). The results demonstrate that the new force field effectively replicates both the monopoles and the energies. In comparison to ReaxFF, the new force field exhibits comparable or superior performance. Furthermore, molecular dynamics simulations of n-heptane decomposition effectively reproduce the primary products and reactions observed in the experiments. Given the simplicity and physically motivated nature of the model, it is expected that the new force field will be utilized in future studies to investigate chemical reaction mechanisms involving more elements.

Construction of Au nanoparticles decorated on ZnFe2O4@ZnIn2S4 core-shell structure to enhance photocatalytic hydrogen production

Developing effective photocatalysts for water splitting is essential to generating H2 energy sources. Herein, a novel ZnFe2O4@ZnIn2S4/Au ternary composite (abbreviated as ZFO@ZIS/Au) was successfully designed and fabricated by loading Au nanoparticles on the ZFO@ZIS surfaces for effective photocatalytic H2 generation for the first time. Attributed to the synergistic effect of the traditional II-type heterojunction charge transfer and Au nanoparticles as co-catalysts, the ZFO@ZIS/Au heterojunction generated greater amounts of hydrogen under visible light irradiation. The ZFO-7%@ZIS/Au-2 catalyst displayed the highest H2 production rate of 1145.38 μmol∙g-1∙h-1, which was almost 3.87 times more than the ZIS value. Furthermore, several characterization techniques were performed to investigate the catalysts and evaluate the catalyst's photocatalytic activity when exposed to visible light. Lastly, a detailed discussion of the corresponding photocatalytic H2 production process of the as-prepared ZFO@ZIS/Au heterojunction was provided. The distinctive research might offer a potential approach for modifying zinc ferrate for photocatalytic hydrogen production.

Photothermal-assisted S-scheme heterojunction of NiPS3 nanosheets modified ZnIn2S4 microspheres for promoting photocatalytic hydrogen evolution

Exploring high-efficiency photocatalysts for solar hydrogen (H2) generation through water splitting is of great significance for addressing both energy shortage and environmental contamination. In this work, a facile self-assembly strategy was developed to couple NiPS3 nanosheets (NPS NSs) with ZnIn2S4 (ZIS) microspheres to synthesize NPS NSs/ZIS (NPS/ZIS) composites, featuring a characteristic of S-scheme charge transfer mechanism. The NPS/ZIS composites possess broad-spectrum light absorption property, improved photothermal effect and efficient charge transfer, showcasing exceptional solar-to-chemical energy conversion capability for visible-light-driven photocatalytic hydrogen evolution (PHE). The photothermal effect derived from NPS NSs loading can facilitate charge carrier transfer across the interfaces and surface reaction kinetics. By carefully adjusting the mass ratio of NPS NSs, the optimized 4-NPS/ZIS exhibits excellent stability and significantly improved PHE activity (1827.6 μmol⋅g−1⋅h−1) in water, which is 18.4 times higher than that of bare ZIS (99.4 μmol⋅g−1⋅h−1). Furthermore, the 4-NPS/ZIS also shows the high PHE efficiency of 312.2 μmol⋅g−1⋅h−1 in seawater. Diverse characterization results reveal that the remarkably enhanced PHE performance primarily arises from the synergistic effect of S-scheme heterostructure, heightened light harvesting capacity, and enhanced photothermal effect. On the basis of density functional theory (DFT) simulations and experimental verifications, a possible PHE mechanism via the S-scheme heterojunction with photothermal assistance in NPS/ZIS is proposed. This study serves as inspiration for the development of novel photothermal-assisted S-scheme photocatalysts, paving the way for efficient and sustainable green energy production.

DES-driven sustainable dual valorization of lignocellulose into carbon dots and porous biochar for effective wastewater remediation

Deep eutectic solvents (DES) are renowned for their effectiveness in deconstructing lignocellulose and extracting lignin, yet the challenges lie in lignin condensation and the disposal of the DES remnants after pretreatment. To overcome these issues, this work proposed a holistic strategy utilizing deep eutectic solvent (DES)-driven lignocellulose deconstruction to upgrade lignocellulose into nitrogen-doped carbon dots (CDs) and iron-decorated porous carbons, serving as photocatalysts and adsorbents, respectively. These nitrogen-doped CDs via the choline chloride/FeCl3 DES pretreatment exhibited abundant nitrogen/oxygen functional groups, enhancing photocatalytic activities and facilitating effective charge separation and transfer. The photocatalytic efficiency of the CDs on dyes reached 97 % under acidic conditions primarily, and free radical quenching experiments indicated that singlet oxygen was the dominant oxidant species. Moreover, the adsorption capabilities of Fe-decorated porous carbons for Congo red reached 2432.3 mg·g−1, surpassing most existing carbon materials. The adsorption mechanism was due to a synergistic effect including physical adsorption, coordination, hydrogen bonding, electrostatic, and π-π interactions. This study proposed a synergetic conversion of DES and lignocellulose into functional carbon materials for wastewater remediation, which inspired the development of a green and cost-effective biorefinery.

Oxygen enriched PAni-based counter electrode network toward efficient dye-sensitized solar cells (DSSCs)

Dye-sensitized solar cells (DSSCs) have great potential as a renewable energy technology assisting combat climate change due to its low cost, adaptability, and sustainability. Oxygen plasma ion doping is a promising strategy to improve the capacity of a low-cost, platinum-free counter-electrodes (CEs) to absorb photons and drive high-performance DSSCs via generating an abundance of active absorption sites. In this instance, novel PAni–ZnO (PZ) composite layers were designed as a CE material and received various in-situ oxygen plasma dosages, including 0, 2, 4, 6, 8, and 10 min, to improve their physiochemical and microstructural feature for the first time, to the best of our knowledge. Physical evaluations of the microstructure, porosity, morphology, contact angle, roughness, electrical, and optical, electrochemical impedance spectroscopy (EIS) features of CEs were conducted in along with an evaluation of J–V variables. Compared to pristine CE substance, the surface nature of the modified hybrids was gradually enhanced as the plasma level rose, reaching an optimum after 8 min (i.e. 0.2 µm for average pore size and average roughness Ra = 7.21 µm). Expanded plasma treatment doses also improved PV cell performance even further: after 4 min at a plasma level, η = 5.41% was obtained, and after 6 min in a oxygen plasma environment, η = 5.81% was obtained. Mixing high energetic plasma ions increased the mobility of charge carriers in PAni composites along with lowered charge carrier recombination through generating an environment that was conducive to charge dissociation. Therefore, longer lifespans and more effective charge transfer inside the photovoltaic cell as a consequence of the increased mobility less resistive losses. In this respect, following 8 min of plasma surface modification of the PZ CE, the optimized efficiency of 6.31% and Jsc of 15.6 mA/cm2 were obtained. The improvement in efficiency equated to a proportion growth of 77% versus a pristine one. This gain was explained by the reality that suffusing a quantity of oxygen plasma free radicals into the PAni system developed continuous channels that enabled the mixture to move electrons more rapidly, hence raising the photovoltaic efficiency. Overall, this study highlights the advantages of regulating heteroatom species and their co-doping, offering a new perspective for the application of heteroatom-doped CE in DSSCs.

MoS2/porous carbon nanofiber heterostructures for efficient evaporation-driven generators.

Evaporation power generators (EPGs) based on natural water evaporation can directly convert heat energy from the surrounding environment into electrical energy. However, EPGs are difficult to commercialize due to the low charge generation and transport efficiency of single material systems, resulting in unsatisfactory open-circuit voltages and short-circuit currents. Here, we step by step prepared MoS2/porous carbon nanofiber (PCNF) heterogeneous systems by electrospinning and hydrothermal methods. Electron microscope measurements proven the uniform coating of high-crystalline quality MoS2 nanosheets on PCNF fabrics, and the uneven concave-convex surface increased the specific surface area. MoS2 covered PCNF fabrics retained good hydrophilicity, which was suitable for absorbing water and keeping the surface wet during long-term evaporation. Moreover, layered MoS2 with rich surface charge improved the charge transfer of the MoS2/PCNF fabrics. As a result, the open-circuit voltage and short-circuit current of the EPGs prepared with MoS2/PCNF fabrics were improved to 0.25 V and 75 μA, respectively, compared with those based on PCNF fabrics, which demonstrated that the MoS2 coatings improved the interaction area with water and the charge transfer effect of the EPGs. This heterogeneous combination strategy provides ideas for the preparation of high-performance EPG materials.&#xD.

Dissecting the hydrogen bond network of water: Charge transfer and nuclear quantum effects

The molecular structure of water is dynamic, with intermolecular (H)-bond interactions being modified by both electronic charge transfer and nuclear quantum effects (NQEs). Electronic charge transfer and NQEs potentially change under acidic / basic conditions, but such details have not been measured. Here, we developed correlated vibrational spectroscopy, a symmetry-based method that distinctively separates interacting from non-interacting molecules in self- and cross-correlation spectra, giving access to previously inaccessible information. We found that OH − donated ~8% more negative charge to the H-bond network of water and H 3 O + accepted ~4% less negative charge from the H-bond network of water. D 2 O had ~9% more H-bonds compared to H 2 O, and acidic solutions displayed more dominant NQEs than basic ones.

Diatomic Active Sites Embedded Graphyne as Electrocatalysts for Ammonia Synthesis.

Ammonia (NH3) is a vital chemical compound in industry and agriculture, and the electrochemical nitrogen reduction reaction (eNRR) is considered a promising approach for NH3 synthesis. However, the development of eNRR faces the challenge of high overpotential and low Faradaic efficiency. In this work, graphyne (GY) is anchored by 3d, 4d, and 5d dual transition metal atoms to form diatomic catalysts (DACs) and is roundly investigated as an electrocatalyst for eNRR via density functional theory calculations. Due to the protrusion of anchored metal atoms, the active sites of GY are better exposed compared to other substrates, exhibiting higher activity. Through four-step hierarchical high-throughput screening (ΔG*N2 < 0 eV, ΔG*N2→*N2H < 0.4 eV, ΔG*NH2→*NH3 < 0.4 eV, and ΔG*N2 < ΔG*H), the number of selected catalysts in each step is 325, 240, 145, and 20, respectively. Considering a series of factors, including stability, initial potential, and selectivity, 13 kinds of eligible catalysts are identified. Optimal eNRR paths studies show that the best catalyst Mn2@GY features no onset potential. For the three catalysts (Mn2@GY, Ir2@GY, and RhOs@GY), the onset potentials of the most favorable eNRR pathways are -0.07, -0.12, and -0.17 V, respectively. The excellent catalytic activity can be credited to the effective charge transfer and orbital interaction between the active site and adsorbed N2. Our work demonstrates the significance of DACs for ammonia synthesis and provides a paradigm for the study of DACs even for other important reactions.

Porphyrinoid-Functionalized ZnO Nanoflowers for Visible Light-Enhanced and Selective Benzylamine Detection at Room Temperature.

Functionalization of hybrid organic molecules as layers on ZnO nanoflowers (NFs) gives an excellent combination of sensing toward visible light and vapors of various volatile organic compounds (VOCs). In this work, hybrid organic molecules functionalized ZnO NFs were utilized for the photoinduced detection of benzylamine at room temperature. The ZnO NFs were synthesized via a facile solution route and functionalized with four different porphyrin-conjugated molecules namely (i) pyrene-porphyrin (PP), (ii) pyrene- porphyrinato zinc (ZnPP), (iii) triphenylamine- porphyrin (TP) and (iv) triphenylamine- porphyrinato zinc (ZnTP). The diameter of the flower-like structure was found to be ∼3.2 μm with the thickness of petals being ∼24.1 nm. The gas adsorption performance of the functionalized ZnO NFs on light activation at room temperature was studied by using a scanning Kelvin probe (SKP) system. The improved adsorption properties of the samples can be attributed to the heterojunctions and light activation. In particular, an enhanced response of ZnTP functionalized ZnO (ZnTPZ) toward benzylamine was observed. Further, static gas sensing experiments using ZnTPZ under various concentrations (1, 3, 5, 10, 15, and 25 ppm) of benzylamine vapors both in dark and visible light conditions have exhibited a linear increase in the response. The selectively enhanced response of ZnTPZ compared to that of pristine ZnO was thus confirmed at 1 ppm of benzylamine. The sensitivity and limit of detection of the ZnTPZ sensor were calculated to be 0.0292 ppm-1 and 197 ppb, respectively. The coordination metal (Zn) has helped in effective charge transfer between benzylamine and ZnTPZ by providing additional active sites for interactions. Also, density functional theory calculations demonstrated the role of the hybrid organic molecules on the sensor surface in improving gas adsorption. Further, fresh cabbage was utilized for real sample analysis with the proposed sensor under visible light illumination conditions, and a linear response was obtained for low ppm evaluation at room temperature. Overall, the obtained results suggest the development of novel ZnTPZ-based light-activated gas sensors for low ppm benzylamine detection at room temperature. These kinds of sensors can be used to track the freshness of vegetables as they are transported from farms to commercial outlets.

Effect of Peripheral Functionalization of Pt(II) Porphyrin(2.1.2.1) on Singlet Oxygen Generation.

Four structurally bent porphyrin(2.1.2.1) Pt(II) complexes have been obtained and verified well. Main absorbance of Pt(II) porphyrin(2.1.2.1) displayed a significant red-shift compared to that of porphyrin(1.1.1.1) Pt(II) molecules. 1O2 study indicated that electron-withdrawing group and intramolecular charge transfer effect synergistically endowed Pt(II) porphyrin(2.1.2.1) with good singlet oxygen-sensitizing capacity under blue LED light irradiation. This work presents a simple synthesis way to develop a new series of efficient porphyrinoid singlet oxygen photosensitizers for PDT through molecular engineering.

High‐performance triboelectric nanogenerators boosted by synergistically aligned piezoelectric/conductive composite nanofibers

AbstractTo address the need for efficient, flexible, and wearable power sources for portable electronics, a high performance triboelectric nanogenerator (TENG) was proposed by incorporating vertically‐aligned barium titanate (BaTiO3)/antimony tin oxide (ATO) nanofibers in polydimethylsiloxane (PDMS) negative triboelectric layer, where BaTiO3 served as piezoelectric material, and ATO served as conductive filler. Silver‐coated conductive fabric was used as electrode to ensure integrability and wearability. By strategically coupling the triboelectric effect of PDMS, the piezoelectric effect of BaTiO3 nanofibers, and the charge transfer effect of ATO nanofibers, the TENG exhibited the optimum output voltage and current of approximately 119 V and 28 μA, and power density of 11.74 μW/cm2, respectively. This device demonstrates its potential applications in energy supply by effectively illuminating 174 commercial green LEDs and charging capacitors for powering electronics. Additionally, the successful integration of the TENG into a smart fencing jacket highlights its utility in practical applications.Highlights TENGs with vertically‐aligned BaTiO3/ATO composite nanofibers was constructed. The output performance of TENGs were enhanced by coupling triboelectric and piezoelectric effects. Conductive ATO nanofibers were incorporated to enhance charge transfer for performance enhancement. A smart fencing jacket with scoring system was developed using the wearable TENG.

Optimization, imaging and LHE analysis of magnesium oxide nanoparticles synthesized with carambola extract as natural dye sensitizer

This work explores the enhancement of dye-sensitized solar cells (DSSCs) by using magnesium oxide nanoparticles (MgO NPs) that have been green-synthesized, with carambola extract acting as a natural dye sensitizer. Green synthesis minimizes the negative effects of traditional synthesis methods on the environment by providing a sustainable and ecologically friendly way to produce MgO NPs. To increase their effectiveness in DSSC applications, the synthesized nanoparticles underwent optimization. The morphology and size distribution of MgO NPs were characterized by scanning electron microscopy (SEM), which revealed spherical forms with a consistent size distribution. The crystalline nature of the MgO NPs was verified by X-ray diffraction (XRD), which revealed distinctive peaks that correspond to the bulk MgO crystal planes. A band gap of 3.5 eV, appropriate for UV region absorption, was found using UV–visible spectroscopy. FT-IR (Fourier-transform infrared) spectroscopy revealed information about their molecular compositions. Positive electronic characteristics, such as a negative total energy change (ΔE_T) and a high electrophilicity index (ω), which indicates effective charge transfer, were found through computational analysis. The light harvesting efficiency (LHE) value of 0.00459 signifies optimal light absorption capability by the dye molecule. The outcomes show that MgO NPs that have undergone green synthesis have the potential to be efficient and stable sensitizers for DSSCs. In addition to highlighting the significance of green synthesis techniques in nanomaterial research for renewable energy applications, this work advances the development of efficient and sustainable solar energy systems.

Amplifying the photovoltaic properties of tetrathiafulvalenes based materials by incorporation of small acceptors: a density functional theory approach

Currently, polycyclic aromatic compounds in organic solar cells (OSCs) have gained substantial consideration in research communities due to their promising characteristics. Herein, polycyclic aromatic hydrocarbons (PAHs) core-based chromophores (TTFD1-TTFD6) were designed by structural modifications of peripheral acceptor groups into TTFR. The density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculations were carried out at B3LYP/6-311G (d, p) functional to explore insights for their structural, electronic, and photonic characteristics. The structural modulation unveiled notable electronic impact on the HOMO and LUMO levels across all derivatives, leading to decreased band gaps. All the designed compounds exhibited band gap ranging from 2.246 to 1.957 eV, along with wide absorption spectra of 897.071-492.274 nm. An elevated exciton dissociation rate was observed due to the lower binding energy values (Eb = 0.381 to 0.365 eV) calculated in the derivatives compared to the reference (Eb = 0.394 eV). Furthermore, data from the transition density matrix (TDM) and density of states (DOS) also corroborated the effective charge transfer process. Comparable results of Voc for reference and designed chromophores were obtained via HOMOdonor−LUMOPC71BM. The declining Voc order values was noted as TTFD5 > TTFD6 > TTFD4 > TTFD3 > TTFD2 > TTFD1 > TTFR. Interestingly, TTFD5 was found with the smallest energy gap and highest absorption value, resulting in better charge transference among all the derivatives. The results illustrated that the modification in indenofluorene based chromophores with end-capped small acceptors proved to be a significant approach in achieving favorable photovoltaic properties.

Thermo-controlled Water Microenvironment Inducing Fluorescence Enhancement of Chalcone Nanohydrogels for Mitochondrial Temperature Sensing.

Developing aggregation-induced emission (AIE)-based hydrogels that exhibit fluorescence enhancement as to thermal properties is an interesting and challenging task. In this work, we employed the fluorophore 2'-hydroxychalcone (HC), fluorescence properties of which are easily influenced by the excited-state intramolecular proton transfer and twisted intramolecular charge transfer (TICT) effects, to develop a novel type of temperature-sensitive polymers, hydroxychalcone-based polymers (HCPs). By controlling the temperature-dependent water microenvironments in HCPs, the intramolecular hydrogen bonds between water and HCPs can be regulated, thereby influencing the TICT process and leading to thermo-induced fluorescence enhancement, which shows a contrary tendency compared to typical AIEgens that always exhibit fluorescence attenuation as the thermal energy accelerates the molecular motion. Following the decoration with triphenylphosphine, the resulting polymer P-HCP assembled into nanohydrogels and served as a fluorescent probe for intracellular mitochondrial temperature sensing.

Recent innovations in engineering Zinc Oxide (ZnO) nanostructures for water and wastewater treatment: Pushing the boundaries of multifunctional photocatalytic and advanced biotechnological applications

Owing to its rapid advancement in nanotechnology, latest publications (recent 5 years) related to zinc oxide (ZnO) in various aspects and applications have been reviewed. Trend has shifted to the innovation of pristine ZnO nanostructures functionalized with elemental dopants and heterojunction to improve the photoactivities on micropollutant degradation and heavy metals removal as well as the antibacterial effect towards microorganisms. The fundamentals of improved photoactivities (i.e., low recombination rate of charge carrier and effective charge transfer) and enhanced antibacterial properties (i.e., dissolution of ions and generation of reactive oxygen species) are accentuated. Subsequently, a detailed examination is undertaken to elucidate the key impacts of ZnO on actual wastewater treatment systems. This review concludes with a consolidated overview on the recent advances of ZnO for environmental wastewater decontamination and the future prospects on tailoring ZnO based on their photocatalytic and antibacterial properties to match various expectations from practical applications while minimising the adverse impacts on surrounding environment.

Synthesis and design strategies of codoped titanium dioxide with band alignment and multiple reflections of incident light for efficient visible light activity

To increase the visible-light photocatalytic performance of Titania, it was codoped with specific elements and was effectively synthesized. The goal of enhancing visible-light photocatalytic performance was achieved by broadening its absorption spectrum in the visible light range and enhancing the quantum efficiency of the photocatalytic reaction toward the degradation of the hazardous dye methyl orange. Mixed phase photocatalyst with different percentage hierarchical secondary nanostructure has been synthesized by the combination of chemical bath deposition methods and hydrothermal. The density of the sprout-like branches changes from the concentration levels of titanium butoxide in the precursor solution. Based on the experimental analysis, a mechanism was proposed to interpret the evolution of the secondary growth. The band edge difference between anatase and TiO2(B) phases induces transfer of charge at the interface. The result revealed that in the TiO2 crystal some O-sites were substituted by N and S anions resulting in band mixing and incorporation of extra energy states in between the valence band maxima and conduction band minimum, which caused a shift towards longer wavelengths in the absorption edge. Compared with pure TiO2 nanobelt, the surface modified doped samples exhibited good visible light activity. The combined effect of fast charge transfer in the atomic level contact between two phases and localized N 2p and S 3p band above valence-band edge in the same material makes titanium dioxide suitable for use in the presence of visible light.

Improved Electrode Performance Using Fine‐Tuned Poly(arylene piperidinium) Ionomers In Anion Exchange Membrane Fuel Cells

AbstractIonomers based on poly(arylene piperidinium)s with varying ion exchange capacities are evaluated in different combinations of anode and cathode electrodes in anion exchange membrane fuel cells. The operational conditions are chosen with an asymmetrical regime including a dry anode with 50% relative humidity at the inlet, and full humidification at the cathode. Polarization and impedance measurements are carried out in potentiostatic steps within 0.3–0.9 V and distribution of relaxation times analysis is utilized to deconvolute resistance contributions. The results show that the best cell performance is achieved with both electrodes utilizing an ionomer with the highest ion exchange capacity (IEC) of 2.79 meq g−1. Cells built exclusively from this ionomer achieved a peak power density of 1.01 W cm−2. Deconvolution of the resistance contributions revealed the impact of water content on the effective charge transfer resistance in both electrodes and a diffusion resistance associated with the movement of water from anode to cathode side. The higher conductivity and water uptake of the high IEC ionomer resulted in a reduction of both resistance contributions, leading to the highest performance under the conditions evaluated. These findings provide important insights into how to tailor the electrode layers for optimum fuel cell output.